CN1197819A - 热固性树脂组合物 - Google Patents
热固性树脂组合物 Download PDFInfo
- Publication number
- CN1197819A CN1197819A CN98108759A CN98108759A CN1197819A CN 1197819 A CN1197819 A CN 1197819A CN 98108759 A CN98108759 A CN 98108759A CN 98108759 A CN98108759 A CN 98108759A CN 1197819 A CN1197819 A CN 1197819A
- Authority
- CN
- China
- Prior art keywords
- structural unit
- diamines
- polyimide
- polycarbodiimide
- thermosetting resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 13
- 239000011342 resin composition Substances 0.000 title abstract description 5
- 239000004642 Polyimide Substances 0.000 claims abstract description 38
- 229920001721 polyimide Polymers 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 150000004985 diamines Chemical group 0.000 claims description 38
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- -1 siloxane backbone Chemical group 0.000 description 20
- 150000008064 anhydrides Chemical class 0.000 description 17
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
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- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 2
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Abstract
本发明公开了一种用于固定处理电子部件的热固性树脂组合物,它能够在低温下短时粘合,具有耐热性,低吸湿性,且几乎不会产生包装开裂等问题。该热固性树脂组合物包含混合在一起的可溶于有机溶剂的聚碳化二亚胺和可溶于有机溶剂的硅氧烷改性的聚酰亚胺。
Description
本发明涉及一种新型热固性树脂组合物。本发明的热固性树脂组合物用作固定处理电和电子部件如半导体基片的粘合剂。
浆状粘合剂和将粘合剂涂布于耐热性材料上的产品已为公知的用作固定处理电和电子部件如半导体基片、基板和铅框的粘合剂。热固性树脂如环氧树脂、丙烯酸树脂和橡胶-酚树脂已被用作这种粘合剂,但是,它们需要通过加热进行长时高温固化处理,并且粘合剂的工作性能较差。此外,还存在一些其它问题,经加热固化时,会产生大量的含有铅的挥发性组分;由于其高吸湿性,经逆流焊接,会产生开裂。因此,对于固定处理电和电子部件而言,常规的粘合剂还不能说具有很高的可靠性,迄今为止,还没有令人满意的粘合剂可供使用。
另外,使用热塑性聚酰亚胺树脂的热熔体型膜粘合剂可通过加热在短时内粘合,在粘合后无需附加的固化过程。但是,因其玻璃化温度高,为进行加工需要很高的温度,从而很可能对被粘物造成热损害。
另一方面,当使用低玻璃化温度的粘合剂以赋予低温加工性能时,存在的问题是耐热性较差,且可靠性大为降低。例如,聚碳化二亚胺的玻璃化温度低,其具有优良的粘合性及低温加工性,但其可靠性很差,当将其置于高温和高压的气氛下几十小时时,会失去粘合强度。为了解决聚碳化二亚胺的这一问题,可向其分子中引入硅氧烷骨架以改善其可靠性。然而,大多数市售用作单体原料的硅氧烷改性的二异氰酸酯为脂族物质,因而,存在的问题就是在生产聚碳化二亚胺时它们具有活性。进而,硅氧烷改性的芳族二异氰酸酯通常很难合成,且产品不稳定导致不能实际使用。因而,仍希望通过使聚碳化二亚胺与其它聚合物掺混而非单独使用聚碳化二亚胺来改善耐湿性。
通过使聚碳化二亚胺与二芳基取代的nadiimide掺混,可改善物理性能。JP-A-7-286140(本文术语“jp-A”是指“未审日本专利申请”)公开了具有优良耐热性的热固性涂料,其包含上述nadiimide。JP-A-7-258353公开了一种树脂组合物,包含上述nadiimide和bismaleimide的掺混物。JP-A-7-330872公开了树脂组合物,其包含上述nadiimide和环氧树脂的掺混物。但是,当其用作粘合剂时,粘合强度和柔性并未达到令人满意的程度。
进而JP-A-62-1714、5-239427和5-320611均公开了通过掺混环氧树脂与聚碳化二亚胺树脂得到的粘合树脂组合物。但是环氧树脂的贮存稳定性与吸湿性仍存在问题,仍未能达到满意的结果。
另一方面,虽然聚酰亚胺通常具有优良的耐热性,但在许多情形下它们不能溶解于有机溶剂中,因而不能与聚碳化二亚胺掺混。通常,它们常以聚酰胺酸的形式使用,聚酰胺酸为聚酰亚胺的前体,从而改善聚酰亚胺与其它聚合物的掺混性。然而,当欲与其混合的聚合物为聚碳化二亚胺时,存在的问题是它会与聚酰胺酸中的羧基反应,使得溶液的稳定性大大变劣。
经过深入研究,得到了一种能够在低温下只需很短时间即可粘合的树脂组合物,其耐热性好,吸湿性低,并且很少会产生包装开裂。结果发现可优选混合可溶性聚酰亚胺与可溶性聚碳化二亚胺树脂。据此,完成了本发明。
因而,本发明的一个目的是提供了一种树脂组合物,其包含可溶于有机溶剂的聚碳化二亚胺和可溶于有机溶剂的聚酰亚胺。
本发明的另一个目的是提供了一种粘合片,其单独包含热固性树脂组合物,或者包含一种载体及设于其上面且为片状形式的热固性树脂组合物。
其中Rsi为硅氧烷二胺残基;R10为二胺残基;R20为酸二酐(aciddianhydride)残基;(m+n)为6-200的整数,也包含二胺和/或含有下式(4)表示的基团的酸二酐结构单元:其中,X为氢原子或氟原子。(1)聚碳化二亚胺
如果I小于2,经注塑成膜或类似物后其可靠性较差,而如果I大于400,则溶液的贮存稳定性差,并且溶液在实际使用时不可能耐久。
在磷型催化剂存在下,通过常规方法聚合相应的二异氰酸酯可制得聚碳化二亚胺。
二异氰酸酯也可以采用常规方法制备。例如,相应的诸如2,2-双[4-(4-氨基苯氧)苯基]丙烷(BAPP)或2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(BAPF)的二胺被用作前体,这些二胺可用光气、碳酸二苯酯、三甲基氯代硅烷等进行异氰酸酯化。另外,相应的二元羧酸也可用作该异氰酸酯的前体,然后用库尔提斯降解进行异氰酸酯化。
在通过聚合二异氰酸酯生产聚碳化二亚胺过程中,可以单独使用一种二异氰酸酯,或者该二异氰酸酯与其它的二异氰酸酯进行共聚,其用量为60moi%或更少,在此范围内,性能不会变劣。可用于共聚的二异氰酸酯为芳香族二异氰酸酯,其实例为1,3-或1,4-双(4-异氰酸根合苯氧基)苯、2,4-或2,6-亚甲苯基二异氰酸酯、4,4’-二异氰酸根合-2,2’-二甲基或双(三氟甲基)联苯、二异氰酸根合二苯基甲烷、1-甲氧基苯基-2,4-二异氰酸酯、3,3’-二甲氧基-4,4’-二苯基甲烷二异氰酸酯、4,4’-二苯基醚二异氰酸酯、3,3’-二甲基-4,4’二苯基醚二异氰酸酯和邻亚甲苯基二异氰酸酯,但本发明对其并无限定。
用于聚合二异氰酸酯的催化剂可为常规的磷催化剂。例如,可采用phosphorene氧化物中的任一种,例如,1-苯斟-2-phosphorene-1-氧化物、3-甲基-2-phosphorene-1-氧化物、1-乙基-2-phosphorene-1-氧化物、3-甲基-1-苯斟-2-phosphorene-1-氧化物和其3-phosphorene异构体。以1mol二异氰酸酯,催化剂的用量通常为0.1-20mol%,优选为0.3-10mol%,更优选0.5-5.0mol%。如果催化剂的用量太小,在反应过程中其会失活,并且反应会停止。而如果催化剂的用量太大,则难于控制反应。
聚合过程中的反应温度通常为50-200℃,优选-10-150℃,更优选20-120℃。根据所采用的二异氰酸酯和溶剂,可适当地改变反应温度。如果反应温度太低,反应根本不可能进行。另一方面,如果温度太高或加热时间太长,可能会发生不希望的副反应,或者产物会分解。因此,建议反应温度通过IR等追踪反应而逐渐地从低温开始升温。
所用的反应溶剂可为任一种溶剂,只要它能够溶解或悬浮二异氰酸酯。溶剂的实例为醚化合物四氢呋喃、二噁烷或二乙醚;卤代烃如二氯甲烷、氯仿、二氯乙烷或四氯乙烷;酮如丙酮、甲乙酮、甲基异丁基酮或环已酮;芳烃如甲苯、二甲苯或苯。这些溶剂可以单独使用或组合使用。如果需要和必要的话,在反应过程中可部分或全部替换溶剂,从而改变反应温度。
反应混合物中的二异氰酸酯的浓度为1-50wt%,优选5-40wt%,更优选10-30wt%。如果浓度太低,反应时间会更长,这是不现实的。另一方面,如果浓度太高,则可能产生副反应,或者反应过程将不能进行控制,这不是一种优选方式。(II)聚酰亚胺
本发明的树脂组合物中的第二种组分为可溶于有机溶剂的聚酰亚胺。优选的聚酰亚胺包含六氟异亚丙基结构或式(4)表示的异亚丙基结构,并包含在式(2)中Rsi表示的硅氧烷结构单元。因此,优选的聚酰亚胺为
(a)包含由下式(2)和(3)表示的重复单元的酰亚胺:其中Rsi表示硅氧烷二胺残基;R10表示二胺残基;R20表示酸二酐残基;(m+n)为6-200的整数;
(b)在二胺结构单元中硅氧烷改性的二胺结构单元的含量为10-100%;和
(c)包含由下式(4)表示的六氟异亚丙基结构或异亚丙基结构二胺和酸酐结构单元的总量(b)与除硅氧烷改性的二胺结构单元之外的酸二酐结构单元和二胺结构单元的总量(a)之比,即b/a,为10-100%,其中X表示氢原子或氟原子。
具有这种结构的聚酰亚胺可很好地与聚碳化二亚胺混溶,使形成的树脂组合物与基片间粘合良好。
此外,如果(m+n)值低于上述范围,则树脂的可靠性会降低,而如果该值大于上述范围,则混溶性会变差。
单体如下所述,引入下述(i)和(ii)其是必要的
(i)一种具有由式(2)表示的硅氧烷结构的硅氧烷改性的二胺;和
(ii)由式(4)表示的结构单元异亚丙基或六氟异亚丙基结构,它在本发明的可溶性聚酰亚胺链中的基本结构。(i)硅氧烷改性的二胺
用于向聚酰亚胺中引入硅氧烷结构(Rsi:硅氧烷二胺残基)的硅氧烷改性二胺优选为由下式(5)表示的二氨基聚硅氧烷:其中R1和R2分别为二价烃基;R3-R6分别为1-6个碳原子的烃基,优选甲基或乙基;k为1-20的整数,优选1-6。R1和R2优选为包含亚甲基链的亚烷基,芳族二价基团的亚芳基,R1和R2更优选为相同的基团。二氨基聚硅氧烷化合物的具体实例为下述二胺
这些硅氧烷改性的二胺可以单独使用或以两种或多种混合的形式使用。在二胺结构单元中硅氧烷改性的二胺结构单元的含量为10-100mol%,优选20-80mol%。如果硅氧烷改性的二胺结构单元的含量小于上述值,则混溶性与粘合性的改进不足,而如果大于上述值,则从经济上考虑是不合算的。(ii)引入式(4)结构单元的单体
下面解释引入由上式(4)表示的异亚丙基结构单元或六氟异亚丙基结构单元的单体。
引入这些结构单元的单体实例为下述除硅氧烷改性二胺之外的二胺,及羧酸二酸酐。
(ii-a)除硅氧烷改性二胺之外的二胺(其引入二胺残基,即R10)。
这种二胺的实例为2,2-双[4-(3-氨基苯氧基)苯基]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、2,2-双[4-(3-氨基苯氧基)苯基]六氟丙烷和2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷。
(ii-b)羧酸二酸酐(其引入酸二酐残基,即R20)
四羧酸二酸酐的实例为2,2-双(2,3-或3,4-二羧基苯基)丙烷二酸酐和2,2-双(2,3-或3,4-或3,4-二羧基苯基)六氟丙烷二酸酐。
羧酸二酸酐结构单元和具有由式(4)表示的结构单元的二胺结构单元的总量(b)与除硅氧烷改性的二胺结构单元之外的酸二酐结构单元和二胺结构单元的总量(a)之比为10-100mol%,优选30-100mol%。如果(b/a)值小于10%,则聚碳化二亚胺与其不能相溶。(iii)其它二胺组分(其引入除上之外的R10)
与上述二胺组分一起使用的其它二胺组分可以为任一种芳族二胺。芳族二胺的实例为对或间亚苯基二胺、4,4’-、3,4’、2,4’或3,3-二氨基二苯基醚,4,4’-、3,4’或3,3-二氨基二苯基砜,4,4’-、3,4’或3,3’-二氨基二苯基硫化物,4,4’-、3,4’或3,3’-二氨基二苯酮,4,4’-、3,4’或3,3’-二氨基二苯基丙烷,4,4’-、3,4’或3,3-二氨基二苯基六氟丙烷,双[4-(3-或4-氨基苯氧基)苯基]甲烷,1,3-双(3-氨基苯氧基)苯,4,4’-双(4-氨基苯氧基)联苯,双[4-(3-或4-氨基苯氧基)苯基]砜和双[4-(3-或4-氨基苯氧基)苯基]醚。它们可以单独使用或以两种或多种混合物形式使用。式(iv)其它酸酐(其引入除上之外的R20)
其它的酸酐为除具有上述式(4)表示的结构单元的四羧酸二酸酐之外的四羧酸二酸酐。这种可用于与上述二胺组分反应的羧酸二酸酐的实例为1,2,4,5-苯四酸二酸酐、2,2’,3,3’-或3,3’,4,4’-联苯四羧酸二酐、氧联邻苯二甲酸二酸酐、2,2’,3,3-二苯酮四羧酸二酸酐、或3,3’,4,4-二苯酮四羧酸二酸酐、2,2-双(3,4-二羧基苯基)砜二酸酐、双(2,3-或3,4-二羧基苯基)甲烷二酸酐、2,3,6,7-萘四羧酸二酸酐、1,4,5,8-萘四羧酸二酸酐、双(2,3-或3,4-二羧基苯基)二氟甲烷二酸酐、1,3-双(3,4-二羧基苯基)-1,1,3,3-四甲基二硅氧烷和其衍生物。它们可以单独使用或以两种或多种的混合物形式使用。[聚酰亚胺的生产方法]
可溶于有机溶剂的聚酰亚胺可以按照常规方法合成。即,上述二胺与几乎等摩尔量的四羧酸二酸酐在一种溶剂中反应,制备聚酰胺酸(聚酰亚胺的前体),通过加热或化学手段使聚酰胺酸酰亚胺化以得到聚酰亚胺。
例如,化学酰亚胺化方法为,将诸如二氯己基碳化二亚胺、三氟乙酸酐、亚硫酰二氯或三氯化磷的脱水剂加入聚酰胺酸中,使形成的混合物在搅拌下进行闭环反应,如果需要的活,同时进行冷却。对形成的反应混合物过滤,得到的滤液倒入沉淀剂如2-丙醇中以沉淀出反应产物。滤出沉淀,洗涤,干燥,得到所需聚酰亚胺粉末。
另一方面,可以在150℃或更高的温度下通过加热聚酰胺酸的溶剂来进行酰亚胺化过程,以完成脱水闭环反应。为了有效地将副产物水从体系中除去,可同时加入溶剂如二甲苯或甲苯。此外,使用有机碱如三乙胺、异喹啉或吡啶可促进酰亚胺化率。通过加热法酰亚胺化制备的聚酰亚胺可以直接使用,也可以在随后通过再溶解于有机溶剂在2-丙醇或甲醇中沉淀而形成粉末再使用。
可用于上述聚合反应的有机溶剂包括N-甲-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、1,3-二甲基-2-咪唑啉酮、二甲基亚砜、二甲基硫、二甲基砜、吡啶、四甲基脲、二甘醇二甲醚、三甘醇二甲醚、四氢呋喃、二噁烷和环己酮。它们可以单独使用或组合使用。
如果需要和必要的活,本发明的可溶性聚酰亚胺可采用邻苯二甲酸酐或其衍生物或苯胺或其衍生物进行端封。(组合物的制备)
本发明包含聚碳化二亚胺作为主要组分的树脂溶剂可以用向聚碳化二亚胺溶液中加入并溶解可溶性聚酰亚胺粉或者先将可溶性聚酰亚胺粉末溶解于有机溶剂中,再将形成的可溶性聚酰亚胺的溶液的聚碳化二亚胺混合进行制备。所用的有机溶剂可以为任何能够溶解可溶性聚酰亚胺和聚碳化二亚胺的有机溶剂。具体而言,可采用用于上述聚合过程的相同的有机溶剂。
以100重量份的作为主组分的聚碳化二亚胺计,本发明的树脂组合物中可溶性聚酰亚胺的量为0.1-50重量份,优选1-30重量份,更优选2-20重量份。如果可溶性聚酰亚胺量太少,其内在性能不可能展现出来。另一方面,如果其太大,就会失去聚碳化二亚胺的特性如低Tg和低吸湿性。此外,树脂中也可能发生相分离。
本发明的耐热性树脂组合物可与微细的无机填料混合,其用量应不会损害树脂组合物的加工性和耐热性。此外,如果需要的话,可加入各种添加剂如消泡剂、匀涂剂或用于使表面平滑的平滑剂。(粘合片)
包含本发明的聚碳化二亚胺作为主要组分的清漆可按照常规方法制成膜,从而得到粘合片。该粘合片的厚度通常为1-2000um,但该厚度并非限定性的,它可根据粘合剂用途进行适当地选择。另外,粘合片的形状和大小也可根据被粘物如铅框或半导体基片进行适当地改变。
如果需要的话,如为了赋予导电性,改善热传导及控制弹性,特别是实现高弹性,在形成粘合片时,可以掺混一种或多种无机粉末,包括金属或合金(如铝、铜、银、金、镍、铬、铅、锡、锌、钯和焊剂)、陶瓷(如氧化铝、二氧化硅、氧化镁和氮化硅)、碳等。
膜的涂布温度为20-300℃,优选50-250℃,更优选70-200℃。如果涂布温度低于20℃,溶剂还会残余于膜中,而如果该值高于300℃,则膜可能会热固化。
进而,可在载体上形成膜。在这样构造的粘合片的制备过程中,清漆可涂布于载体上,或者可将已形成的膜层通过压制等手段压至载体上。
金属箔、绝缘膜等可用作载体。可采用的金属箔的实例包括铝、铜、银、金、镍、铟、铬、铅、锡、锌、钯等。它们可以单独使用或者以包含两种或多种金属的合金使用。绝缘膜可为任一种具有耐热性和耐化学性的膜。其实例包括聚酰亚胺、聚酯、聚对苯二甲酸乙酯等。
金属箔和绝缘膜可以单独使用,或者以两或多层的层压载体形式使用,其具有例如金属箔/绝缘膜的结构,通过层压制备。两层基质的例子为铜/聚酰亚胺两层基质。
本发明的粘合片因通过热处理进行热固化而具有很强的粘合性,同时,得到一种低收湿性固化产品。热处理可以通过适宜的方式进行,如加热器、超声波或紫外线。因而,本发明的粘合片优选可用于对各种材料进行粘合处理,特别优选用于电和电子部件的固定化处理,即对需低吸湿性的半导体基片和铅框处理。
本发明的粘合片具有优良的吸湿性、高柔性、因而易于处理,可很好地粘合半导体元件,并具有优良的贮存稳定性。
通过在金属箔的一个侧面上涂布本发明树脂组合物清漆,再将其干燥而得到的具有粘合剂层的金属箔特别适用于多层线路基质等的生产。
通过下述实施例和比较例进一步说明本发明的热固性树脂组合物。
通过下述方法测量形成的树脂组合物的性能。玻璃化温度(Tg)
采用Seiko ssc/560M(Seiko Corp.生产)将样品从室温加热至400℃,温度升高速度为10℃/分钟。粘合:
将树脂清漆旋涂于硅氧烷片上。使涂布的硅氧烷片在120℃/100%RH的压力蒸煮器(TABAI PRESSURE COOKER TPC-411)中放置。评价热处理前后树脂与硅氧烷片间的接触粘合程度。评价方法是,从100个1mm2的方格上剥离的方格数目被定义为“n”,n/100被用来进行评价(横切测试)。使用ShimadzuAutograph AGS-100D以180°剥离强度测量其粘合强度。
合成实施例1合成聚酰亚胺1:
向备有冷凝器和搅拌器的500ml可分离烧瓶中加入21.72g(42mmol)的2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(BAPF)、10.70g(42mmol)的双(氨基丙基)四甲基二硅氧烷(APDS)和186sg的N-甲基-2-吡咯烷酮(NMP)。在室温及搅拌下,向其中倒入30.02g(84mmol)的2,2双(3,4-二羧基苯基)砜二酸酐。将形成的混合物在室温下搅拌3小时,然后再在180℃下搅拌4小时,以通过加热实现酰亚胺化。得到的清漆在甲醇中再沉,过滤,得到一种粉末。将该粉末在150℃下干燥1小时,再溶解于环己酮中制得一种30wt%的清漆(以下称之为“p11”)。
合成实施例2合成聚酰亚胺2:
按照合成实施例1相同的方法制备聚酰亚胺的清漆(以下称之为“p12”,)只是20.35g(42mmol)的双[4-(3-氨基苯氧基)苯基]砜(3-BAPS)、10.70g(42mm)双(氨基丙基)四甲基二硅氧烷(APDS)用作二胺组分,37.3g(84mmol)的2,2-双(3,4-二羧基苯基)六氟丙烷二酸酐用作酸酐。
合成实施例3合成聚碳化二亚胺:向备有滴液漏斗、冷凝器和搅拌器的101可分离烧瓶中加入800g(1.54mol)的2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(BAPF)、312g(3.09mol)的三乙胺和81的甲苯。通过加热使BAPF完全溶解,再向其中滴加183g(3.09mol)的氯甲酸苯酯。用冰浴使形成的混合物冷却以抑制热量产生,搅拌过液以完成反应。再加入三乙胺(281g;2.78mol),在室温下将置于滴液漏斗中的302g(2.78mol)的三甲基氯代硅烷滴加至其中。完成滴加后,再加入作为碳化二亚胺化的催化剂的29.7g(0.154mol)的3-甲基-1-苯基-2-phosphorene-1-氧化物,将形成的混合物搅拌9小时,同时逐渐升高温度至80℃。在通过IR确认反应完成后,将反应混合物冷却至室温,滤出形成的盐。形成的清漆的溶剂用环己酮替换,得到20wt%的溶液。以下该清漆被称之为“PCD”。
实施例1
将上述p11和PCD以如下表1所示固体比混合制备清漆。每一种清漆产品相互间均能相容而不会相分离。将形成的清漆旋涂于硅氧烷片上,在90℃下干燥30分钟,再在250℃下热处理1小时。然后通过压力蒸煮器测试法(PCT)对耐水性进行测试。表1示出了各个清漆的物理性能和粘合评价结果(横切法)。
表1
清漆组合物 粘合性能清漆号 (重量份数) PCT处理后
PCD PI1 Tg(℃) 初始值 (20小时)1 100 0 150 0/100 100/1002 100 2.5 155 0/100 13/1003 100 5 159 0/100 0/100
实施例2
合成实施例2中合成的PI2用作聚酰亚胺,使其与PCD以表2所示混合比混合制备清漆。这些清漆产品每一种相互间均能相容而不会相分离。以与实施例1相同的方法处理形成的各种清漆产品并对其进行评价。表2示出了各个清漆产品的物理性能和横切法测试结果。
表2
清漆组合物 粘合性能清漆号 (重量份数) PCT处理后
PCD PI2 Tg(℃) 初始值 (20小时)4 100 2.5 150 0/100 20/1005 100 5 153 0/100 0/100
实施例3
将实施1制备的清漆3涂布于铜片上(35μm),在200℃下干燥20分钟,制成一种粘合片(厚度:20μm)。将其粘附在一个42合金片上,它们是在50kg/cm2的压力及350℃下压制2秒粘合的。测量粘合强度,为1,400g/cm。在80℃/90%RH的恒温和恒湿条件下放置后粘合强度为800g/cm。
实施例4
以与实施例3相同的方式对按照实施例2制备的清漆5的粘合强度进行的测试,在常规状态下为1,200/cm。在80℃/90%RH的恒温和恒湿条件下旋转168小时后粘合强度为750g/cm。
比较例1
以与实施例3相同的方式对按照实施例1制备的清漆1的粘合强度进行测试,在常规状态下为1,400g/cm。在80℃/90%RH的恒温和恒湿条件下放置168小时后,出现分离。
比较例2
以与合成实施例1相同的方式制备聚酰亚胺,只是采用3,3-二氨基二苯基砜、双(氨基丙基)四甲基二硅氧烷(APDS)和氧联邻苯二甲酸二酸酐(ODPA)作为单体。形成的聚酰亚胺在与PCD混合时不能与PCD混溶,它们会分离成独立的相。
比较例3
使PCD与聚醚亚胺清漆(由General Elcetric生产)混合。但是,由于它们之间缺乏混溶性,它们分离成独立的相。
本发明的树脂组合物的玻璃化温度为200℃或更低,因而,其低温加工性能得到改善。进而,它能够很好地粘合至被粘物如半导体元件上,并因低吸湿性而具有优异的贮存稳定性,因而可在室温下长期保存。
以上结合具体的实施方案对本发明进行了详细的说明,但本领域的技术人员均可明显地看出,各种变化均不背离本发明的精神和保护范围。
Claims (5)
1、一种热固性树脂组合物,包含可溶于有机溶剂的聚碳化二亚胺和可溶于有机溶剂的聚酰亚胺。
4、一种包含权利要求1、2或3的树脂组合物的膜。
5、一种粘合板,其包含载体和粘合剂层,该粘合剂层包含在该载体的至少一个侧面上形成的权利要求1、2或3的树脂组合物。
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JP2001207055A (ja) * | 2000-01-25 | 2001-07-31 | Nitto Denko Corp | カルボジイミド樹脂組成物 |
JP4522604B2 (ja) * | 2001-03-19 | 2010-08-11 | 日東電工株式会社 | 異方導電性フィルム |
US7129318B2 (en) * | 2003-09-02 | 2006-10-31 | I.S.T. (Ma) Corporation | RTM and RI processable polyimide resins |
KR100687926B1 (ko) | 2005-06-13 | 2007-02-27 | 삼성전자주식회사 | 액정표시장치 |
JP7212626B2 (ja) * | 2017-10-10 | 2023-01-25 | 三井金属鉱業株式会社 | プリント配線板用樹脂組成物、樹脂付銅箔、銅張積層板、及びプリント配線板 |
JP6844570B2 (ja) * | 2018-03-29 | 2021-03-17 | 信越化学工業株式会社 | シリコーンゴム−シリコーン変性ポリイミド樹脂積層体 |
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DE2615343C2 (de) * | 1976-04-08 | 1984-09-27 | Bayer Ag, 5090 Leverkusen | Polymerkombinationen |
JPS621714A (ja) * | 1985-06-28 | 1987-01-07 | Nisshinbo Ind Inc | 熱硬化性樹脂の製造方法 |
JP3713283B2 (ja) * | 1992-02-28 | 2005-11-09 | 日清紡績株式会社 | 耐熱性接着剤組成物 |
JPH05320611A (ja) * | 1992-05-18 | 1993-12-03 | Nisshinbo Ind Inc | フィルム状接着剤組成物 |
EP0708795A4 (en) * | 1993-07-15 | 1996-08-07 | Univ Akron | HEAT-RESISTANT POLYIMIDE MIXTURES AND LAMINATES |
US5576398A (en) * | 1995-07-07 | 1996-11-19 | Japan Synthetic Rubber Co., Ltd. | Thermosetting resin composition |
DE69720593T2 (de) * | 1996-05-29 | 2003-11-27 | Nitto Denko Corp | Aromatisches Polycarbodiimid und daraus hergestellte Folien |
US5830949A (en) * | 1996-09-26 | 1998-11-03 | Nitto Denko Corporation | Adhesive resin composition and adhesive sheet |
-
1997
- 1997-04-04 JP JP9102766A patent/JPH10279799A/ja active Pending
-
1998
- 1998-04-01 EP EP98105988A patent/EP0869151B1/en not_active Expired - Lifetime
- 1998-04-01 DE DE69821664T patent/DE69821664T2/de not_active Expired - Fee Related
- 1998-04-02 US US09/053,782 patent/US6068932A/en not_active Expired - Fee Related
- 1998-04-03 KR KR1019980011746A patent/KR19980081051A/ko not_active Application Discontinuation
- 1998-04-04 CN CN98108759A patent/CN1113937C/zh not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105906813A (zh) * | 2016-06-05 | 2016-08-31 | 吉林大学 | 一种规整嵌段共聚聚酰亚胺硅氧烷单层膜的制备方法 |
CN108864932A (zh) * | 2017-05-11 | 2018-11-23 | 信越化学工业株式会社 | 有机硅改性聚酰亚胺树脂组合物 |
Also Published As
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US6068932A (en) | 2000-05-30 |
CN1113937C (zh) | 2003-07-09 |
EP0869151B1 (en) | 2004-02-18 |
EP0869151A3 (en) | 1998-11-18 |
DE69821664T2 (de) | 2004-07-08 |
JPH10279799A (ja) | 1998-10-20 |
EP0869151A2 (en) | 1998-10-07 |
DE69821664D1 (de) | 2004-03-25 |
KR19980081051A (ko) | 1998-11-25 |
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